Microporous Mg−Si−O and Al−Si−O Materials Derived from Metal Silsesquioxanes

Maxim, Nicolae; Magusin, Pieter C. M. M.; Kooyman, Patricia J.; Wolput, J.H.M.C. van; Santen, Rutger A. van; Abbenhuis, Hendrikus C. L.

doi:10.1021/cm010272g

Cited by 53 publications

(27 citation statements)

References 39 publications

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“…While the formation of micropores by the calcination of POSS molecules has been previously reported [32][33][34][35][36][37][38][39][40][41][42][43][44], an increase in the BET surface area by the calcination of silica-supported POSS was not recognized from the results shown in Table 4, probably because of a low loading level of POSS.…”

Section: Characterization Of the Oxide Catalysts Prepared Using Ti-possmentioning

confidence: 67%

“…In addition to their activities as homogeneous catalysts, their application to heterogeneous catalysis using metal-containing POSS as precursors has been examined [10,13,15,[24][25][26][27][28][29][30][31]. The preparation of microporous silicas containing well-dispersed metal oxide species by the controlled calcination of metal-containing POSS has been reported [32][33][34][35][36][37][38][39][40][41][42].…”

Section: Introductionmentioning

confidence: 99%

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Ti-bridged silsesquioxanes as precursors of silica-supported titanium oxide catalysts for the epoxidation of cyclooctene

Sakugawa

Wada

Inoue

2010

Journal of Catalysis

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ABSTRACT:Silica-supported titanium oxide catalysts were prepared by the controlled calcination of Ti-bridged polyhedral oligomeric silsesquioxanes (POSS) bearing four Si-O-Ti bonds, Ti[(c-C 5 H 9 ) 7 Si 7 O 11 (OSiMe 2 R)] 2 (1a; R = vinyl, 1b; R = methyl) and Ti[(c-C 5 H 9 ) 8 Si 8 O 13 )] 2 (2), supported on various silicas, and these catalysts showed excellent activities for the epoxidation of cyclooctene by t BuOOH as an oxidant to selectively give cyclooctene oxide in high yields. On the other hand, catalysts prepared using a corner-capped-type Ti-containing POSS, CpTi[(c-C 5 H 9 ) 7 Si 7 O 12 ] (3, Cp = cyclopentadienyl), or tetraisopropoxytitanium (4) showed lower activities. The 2 catalysts prepared from Ti-bridged POSS can be easily separated from the reaction mixture and reused without a significant loss of activity. These catalysts were also applicable for the epoxidation of limonene. A spectroscopic study revealed that calcination of Ti-bridged POSS supported on silica gave isolated tetrahedral Ti(IV) species, which would be responsible for the high activity, while calcination of silicasupported 3 or 4 gave aggregated surface titanium oxide species.

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Section: Characterization Of the Oxide Catalysts Prepared Using Ti-possmentioning

confidence: 67%

Section: Introductionmentioning

confidence: 99%

Ti-bridged silsesquioxanes as precursors of silica-supported titanium oxide catalysts for the epoxidation of cyclooctene

Sakugawa

Wada

Inoue

2010

Journal of Catalysis

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“…This method of nanosized catalysts preparation has distinct advantage over traditional methods because the metal atoms remain highly dispersed throughout support [57][58][59]. The study of the Fe-, Cr-, Mg-and Al-containing silicas derived through controlled calcination of appropriate metallsilsesquioxanes showed that nearly homogenous metal dispersion could be achieved [60][61][62]. In the case of Cr-and Fe-containing silicas the small amount of oxide particles was additionally observed.…”

Section: Introductionmentioning

confidence: 99%

Application of POSS Nanotechnology for Preparation of Efficient Ni Catalysts for Hydrogen Production

Исмагилов

Матус

Kuznetsov

et al. 2017

Eurasian Chem. Tech. J.

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POSS (polyhedral oligomeric silsesquioxanes) nanotechnology was applied for preparation of efficient Ni catalysts for hydrogen production through autothermal reforming of methane (ATR of CH 4 ). The novel metal-POSS precursor [Nickel (II) -HeptaisobutylPOSS (C 4 H 9 ) 7 Si 7 O 9 (OH)O 2 Ni] of Ni nanoparticles was introduced into Ce 0.5 Zr 0.5 O 2 support with following calcination and reduction stages of activation. The peculiarity of the genesis of Ni/SiO 2 /Ce 0.5 Zr 0.5 O 2 nanomaterials and their characteristics versus deposition mode were studied by X-ray fluorescence spectroscopy, thermal analysis, N 2 adsorption, X-ray diffraction, high-resolution transmission electron microscopy and H 2 temperature-programmed reduction. The two kinds of supported Ni-containing particles were observed: highly dispersed Ni forms (1-2 nm) and large Ni-containing particles (up to 50-100 nm in size). It was demonstrated that the textural, structural, red-ox and, consequently, catalytic properties of ex-Ni-POSS catalysts depend on the deposition mode. The increase of a portion of difficultly reduced Ni 2+ species is found upon application of intermediate calcination during Ni-POSS deposition that has detrimental effect on the activity of catalyst in ATR of CH 4 . The Ni/SiO 2 /Ce 0.5 Zr 0.5 O 2 catalyst prepared by one-step Ni-POSS deposition exhibits the highest H 2 yield -80% at T = 800 °C.

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“…Polyhedral oligomeric silsesquioxanes have been recognized as well-defined building blocks for nanostructured materials [26][27][28][29][30][31] and some efficient methods of synthesis have also been developed [32][33][34][35][36][37]. ColeHamiltonÕs group reported a number of rhodium metallodendrimers based on polyhedral oligomeric silsesquioxanes cores that give much higher region-selectivity than their small molecule analogues in the hydroformylation reactions.…”

Section: Introductionmentioning

confidence: 99%

Metal nanoparticles stabilized by cubic silsesquioxanes for catalytic hydrogenations

Li¹,

Du²,

Dai³

et al. 2007

Catal Lett

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Octa(diacetic aminophenyl) silsesquioxanes (OAAPS) were synthesized and used as stabilizers for preparing metal (Pt, Pd and Ru) nanoparticles using NaBH 4 as a reducing agent. The synthesized catalysts were characterized by UV-vis, XRD, and TEM. The average diameters of Pt (0), Pd (0) and Ru (0) nanoparticles are 1.6 ± 0.3, 1.4 ± 0.2 and 1.3 ± 0.2 nm, respectively. The metal colloids show excellent stability since OAAPS offer stronger bonding of the cubic linker to the metal nanoparticles through the chelating effect. All colloids prepared are stable and show no precipitation at room temperature for several months. The catalytic hydrogenations of phenyl aldehydes using the metal colloids as catalysts demonstrate that catalytic activities depend on the variety of the metal colloids and the substrates. The colloidal catalysts stabilized by OAAPS can be recycled by simply adjusting the pH of the solution.

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Microporous Mg−Si−O and Al−Si−O Materials Derived from Metal Silsesquioxanes

Cited by 53 publications

References 39 publications

Ti-bridged silsesquioxanes as precursors of silica-supported titanium oxide catalysts for the epoxidation of cyclooctene

Ti-bridged silsesquioxanes as precursors of silica-supported titanium oxide catalysts for the epoxidation of cyclooctene

Application of POSS Nanotechnology for Preparation of Efficient Ni Catalysts for Hydrogen Production

Metal nanoparticles stabilized by cubic silsesquioxanes for catalytic hydrogenations

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